EP0798336A2 - Verfahren zur Dipolymerisation von Polyester - Google Patents
Verfahren zur Dipolymerisation von Polyester Download PDFInfo
- Publication number
- EP0798336A2 EP0798336A2 EP19970300268 EP97300268A EP0798336A2 EP 0798336 A2 EP0798336 A2 EP 0798336A2 EP 19970300268 EP19970300268 EP 19970300268 EP 97300268 A EP97300268 A EP 97300268A EP 0798336 A2 EP0798336 A2 EP 0798336A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- linears
- accordance
- polyester
- depolymerizing
- polyester linears
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- This invention relates to a novel process for depolymerizing polyesters. More particularly, the invention is directed to a process for depolymerizing polyesters by subjecting the polyesters to catalysts, and organic solvents which are substantially free of oxygen and water.
- macrocyclic polyester oligomers have been developed and desired since they have unique properties which make them attractive as matrices for polymer composites. Such desired properties stem from the fact that macrocyclic polyester oligomers exhibit low viscosities, allowing them to impregnate a dense fibrous preform easily. Furthermore, such macrocyclic polyester oligomers melt and polymerize at temperatures well below the melting point of the resulting polymer. Thus, melt flow, polymerization and crystallization can occur isothermally and, therefore, the time and expense required to thermally cycle a tool is favorably reduced.
- the instant invention is directed to a novel process for producing macrocyclic polyester oligomers.
- the novel process comprises the step of contacting in the presence of heat:
- polyester linears employed in the instant invention and described above are poly(alkylene dicarboxylates) and typically of the family consisting of polymeric glycol terephthalates or isophthalates and mixtures thereof including copolyesters of terephthalic and isophthalic acids.
- Especially preferred polyester linears employed in the instant invention are poly(1,2-ethylene terephthalate) (PET) and poly(1,4-butylene terephthalate) (PBT) and copolyesters comprising the same.
- Said copolyesters typically comprise less than about 25% by weight PET but preferably less than about 15% by weight PET.
- Other preferred polyester linears include poly(1,2-ethylene 2,6-naphthalenedicarboxylate) (PEN) and the like.
- titanate compounds which may be employed in this invention are often commercially available and include, for example, alkyl titanates like 2-ethylhexyl titanate, tetrakis-(-2-ethylhexyl) titanate, tetrabutyl titanate and tetraisopropyl titanate, and alkoxy titanates like titanium methoxide, titanium ethoxide and diisopropoxide bis(2,4-pentanedionate).
- Other titanium catalysts which may be employed include glycol titanates like the butanediol titanates disclosed in US patent application RD-24626, the disclosure of which is incorporated herein by reference.
- the desired and resulting macrocyclic polyester oligomers can be separated from the product solution by cooling said product solution to between about 50 to about 120°C and preferably between about 60 to about 100°C to induce precipitation of the linear polyester followed by filtering.
- the macrocyclic polyester oligomers are recovered by evaporation of the resulting filtrate to remove any remaining solvent.
- the recovered macrocyclic polyester oligomers are substantially pure and often at least about 75% pure and preferably at least about 85% pure and most preferably at least about 95% pure.
- the macrocyclic polyester oligomers produced contain less than about 5.0 percent polyester linears and preferably less than about 2.0 percent polyester linears and most preferably less than about 1.0 percent polyester linears.
- Such a reduced level of polyester linears in the macrocyclic polyester oligomers produced is the result, for instance, of the sparging of the organic solvent which allows for the depolymerization to be carried out at higher temperatures. This, in turn, renders it convenient to depolymerize polyester linears while simultaneously decomposing hydroxybutyl terminated oligomers.
- hydroxybutyl terminated oligomers are impurities soluble in organic solvents and typically found when producing macrocyclic polyester oligomers.
- tubular reactors such as those comprising several tubes in parallel with the capacity for reactants to enter one end and products to leave an opposite end are employed for the continuous production of macrocyclic polyester oligomers.
- Heat transfer to such a tubular reactor may be accomplished by means of, for instance, a heating jacket and the reactor may be equipped with a pump to force the flow of reactants and product.
- a continuous stir tank reactor may be employed.
- Such a reactor often comprises stir tank reactors in series or a single reaction vessel divided into a number of compartments.
- the continuous stir tank reactors may be equipped with a heating mechanism, and like the tubular reactors, they may also be equipped with a pump to force the flow of reactants and products as well as a feed tank capable of holding a slurry of reactants and solvent.
- tubular reactor and continuous stir tank reactor mentioned above may be employed, among other reasons, to continuously produce the desired macrocyclic polyester oligomers, and both reactors are described in Chemical Engineers' Handbook, fifth edition, pages 4-20 to 4-22 (1973), the disclosure of which is incorporated herein by reference.
- HPLC high performance liquid chromatography
- mass spectroscopy and molecular weight may be confirmed via gel permeation chromatography.
- the solution was warmed to 100°C and sparged with dry nitrogen until the moisture content of water was about 5 ppm. Sparging also removed the dissolved oxygen in the solvent and inerted the reactor. The reactor was then sealed and the solvent was heated to about 220°C.
- the catalyst was quenched by the addition of water (16.5 moles) by adding the water in an o-xylene mixture.
- the water/o-xylene mixture was pressure transferred into the system, and the system was then allowed to cool to 75° C with stirring in progress.
- the resulting reacted mixture was then filtered through a heated filter. Filtration resulted in removal of the precipitated linear impurities (carboxylic acid terminated linears) from the system.
- the filtrate which contained the desired macrocyclic polyester oligomers was then rotavaped down to about 5ml and then anti-solvent (pentane) was added to induce precipitation of the oligomers.
- the precipitated oligomers were filtered off and dried. Equilibrium was reached after about 10 minutes and yield was determined to be about 55%. Purity of the oligomers obtained was greater than 99%, indicated by no observable hydroxybutyl terminated linears in the product.
- Example 2 was conducted in a manner similar to the one described in example 1 except that 3.42 mole% of catalyst was employed and the reaction temperature was about 240° C. The resulting reaction mixture reached equilibrium after about 10 minutes, yield was approximately 60% and the purity of the macrocyclic polyester oligomer was about 99%, indicated by no observable hydroxybutyl terminated linears in the product.
- Example 3 was conducted in a manner similar to the one described in example 1 except that 2 mole% of catalyst was employed, the reaction temperature was 240°C, a PBT/PET 95:5 (mole ratio) linear copolymer was used and a continuous tubular reactor (having a coiled tube of 80ft in length with an outside diameter of 0.5 inches and an inside diameter of 0.45 inches) was employed in lieu of a stainless steel reactor.
- the resulting macrocyclic copolyester oligomer yield was approximately 60% and the purity of the macrocyclic polyester oligomer was about 99%, indicated by no observable hydroxybutyl terminated linears in the product.
- Example 5 was conducted in a manner similar to the one described in Example 2 except that no sparging with nitrogen took place. Product yield was less than 15%.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US618742 | 1996-03-20 | ||
US08/618,742 US5668186A (en) | 1996-03-20 | 1996-03-20 | Process for depolymerizing polyesters |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0798336A2 true EP0798336A2 (de) | 1997-10-01 |
EP0798336A3 EP0798336A3 (de) | 1997-12-29 |
EP0798336B1 EP0798336B1 (de) | 2003-04-09 |
Family
ID=24478954
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19970300268 Expired - Lifetime EP0798336B1 (de) | 1996-03-20 | 1997-01-17 | Verfahren zur Depolymerisation von Polyestern |
Country Status (5)
Country | Link |
---|---|
US (1) | US5668186A (de) |
EP (1) | EP0798336B1 (de) |
JP (1) | JP3715056B2 (de) |
DE (1) | DE69720579T2 (de) |
ES (1) | ES2193328T3 (de) |
Cited By (8)
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EP1217023A1 (de) * | 1999-10-07 | 2002-06-26 | Kansai Paint Co., Ltd. | Verfahren zur herstellung von olefinharz |
WO2002068496A1 (en) * | 2001-02-28 | 2002-09-06 | E.I. Dupont De Nemours And Company | Manufacture of cyclic ester oligomers |
WO2003080705A1 (en) * | 2002-03-20 | 2003-10-02 | Cyclics Corporation | Catalytic systems |
US6713601B2 (en) | 2000-09-12 | 2004-03-30 | Cyclics Corporation | Species modification in macrocyclic polyester oligomers, and compositions prepared thereby |
US6831138B2 (en) | 2002-01-07 | 2004-12-14 | Cyclics Corporation | Polymer-containing organo-metal catalysts |
US7666517B2 (en) | 2001-06-27 | 2010-02-23 | Cyclics Corporation | Isolation, formulation, and shaping of macrocyclic oligoesters |
US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
US7767781B2 (en) | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
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US6245822B1 (en) * | 1998-04-27 | 2001-06-12 | Matsushita Electric Industrial Co. Ltd. | Method and apparatus for decomposition treating article having cured thermosetting resin |
US6127436A (en) * | 1998-10-26 | 2000-10-03 | Sun Chemical Corporation | Reclaimed poly (ethylene terephthalate) coating |
US7151143B2 (en) * | 2000-01-21 | 2006-12-19 | Cyclics Corporation | Blends containing macrocyclic polyester oligomer and high molecular weight polymer |
US6960626B2 (en) | 2000-01-21 | 2005-11-01 | Cyclics Corporation | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US6369157B1 (en) | 2000-01-21 | 2002-04-09 | Cyclics Corporation | Blend material including macrocyclic polyester oligomers and processes for polymerizing the same |
US6420047B2 (en) | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
KR100779769B1 (ko) * | 2000-09-01 | 2007-11-27 | 시클릭스 코포레이션 | 선형 폴리에스테르를 거대고리 올리고에스테르 조성물로전환시키는 방법 및 거대고리 올리고에스테르 |
JP2002284925A (ja) * | 2001-03-23 | 2002-10-03 | Matsushita Electric Ind Co Ltd | 硬化樹脂の再生方法 |
US6420048B1 (en) | 2001-06-05 | 2002-07-16 | Cyclics Corporation | High molecular weight copolyesters from macrocyclic oligoesters and cyclic esters |
US6436549B1 (en) | 2001-07-16 | 2002-08-20 | Cyclics Corporation | Block copolymers from macrocyclic oligoesters and dihydroxyl-functionalized polymers |
US6787632B2 (en) * | 2001-10-09 | 2004-09-07 | Cyclics Corporation | Organo-titanate catalysts for preparing pure macrocyclic oligoesters |
US6890703B2 (en) | 2002-03-06 | 2005-05-10 | International Business Machines Corporation | Preparation of crosslinked particles from polymers having activatible crosslinking groups |
US20040106713A1 (en) * | 2002-12-03 | 2004-06-03 | Avakian Roger W. | Use of additives in compounds containing macrocyclic poly(alkylene dicarboxylate) oligomers |
US7329703B2 (en) * | 2002-12-20 | 2008-02-12 | Dow Global Technologies Inc. | Polymerized macrocyclic oligomer nanocomposite compositions |
DE10393926T5 (de) | 2002-12-20 | 2006-09-28 | Cyclics Corp. | Reinigung von makrocyclischen Oligoestern |
AU2003293148A1 (en) * | 2002-12-23 | 2004-07-29 | Dow Global Technologies Inc. | Method of smc molding |
US7351769B2 (en) * | 2004-01-26 | 2008-04-01 | Freudenberg-Nok General Partnership | Dynamic vulcanization of elastomers with in-situ polymerization |
US20060128935A1 (en) * | 2004-11-09 | 2006-06-15 | Wilson Tam | Manufacture of macrocyclic polyester oligomers |
JP2008519898A (ja) * | 2004-11-09 | 2008-06-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | N−複素環式カルベンおよび金属アミドまたは金属アルコキシド触媒を使用する巨大環状ポリエステルオリゴマーの重合 |
EP1814929B1 (de) | 2004-11-09 | 2008-09-17 | E.I. Du Pont De Nemours And Company | Polymerisation von makrocyclischen polyesteroligomeren bei erhöhter temperatur mit seltenerdelement-katalysatoren |
US20060141183A1 (en) * | 2004-12-22 | 2006-06-29 | Williamson David T | Polyester clay nanocomposites for barrier applications |
US20060205856A1 (en) | 2004-12-22 | 2006-09-14 | Williamson David T | Compositions of polyesters and sepiolite-type clays |
TWI323737B (en) * | 2005-03-01 | 2010-04-21 | Asahi Kasei Chemicals Corp | Method for producing thermoplastic polymer solution |
EP1879940A1 (de) * | 2005-03-25 | 2008-01-23 | Cyclics Corporation | Herstellung von säurearmem polyalkylenterephthalat und herstellung von makrocyclischem polyesteroligomer daraus |
US7541422B2 (en) | 2005-06-07 | 2009-06-02 | E. I. Du Pont De Nemours And Company | Enzyme-catalyzed process for the preparation of macrocyclic polyester oligomers |
CN101238171A (zh) * | 2005-08-05 | 2008-08-06 | 帝人纤维株式会社 | 从染色聚酯纤维中回收有用成分的方法 |
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WO2008008067A1 (en) | 2006-07-14 | 2008-01-17 | Kimberly-Clark Worldwide, Inc. | Biodegradable aliphatic polyester for use in nonwoven webs |
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JP2008038008A (ja) * | 2006-08-04 | 2008-02-21 | Hitachi Chem Co Ltd | 環状構造高分子及びそれを含む樹脂組成物 |
US20080300355A1 (en) * | 2006-08-25 | 2008-12-04 | Ticona, Llc | Process For Forming Improved Fiber Reinforced Composites and Composites Therefrom |
US8470222B2 (en) | 2008-06-06 | 2013-06-25 | Kimberly-Clark Worldwide, Inc. | Fibers formed from a blend of a modified aliphatic-aromatic copolyester and thermoplastic starch |
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WO2010148188A2 (en) * | 2009-06-19 | 2010-12-23 | Polyone Corporation | Oxygen scavenging terpolymers |
WO2012145065A1 (en) | 2011-02-23 | 2012-10-26 | Cyclics Corporation | Methods for preparation of macrocyclic polyester oligomer via heterogeneous catalysis |
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US9550713B1 (en) | 2015-07-09 | 2017-01-24 | Loop Industries, Inc. | Polyethylene terephthalate depolymerization |
US9815808B2 (en) | 2016-02-29 | 2017-11-14 | Regents Of The University Of Minnesota | Recovery of monomer from polyurethane materials by depolymerization |
US12071519B2 (en) | 2017-09-15 | 2024-08-27 | 9449710 Canada Inc. | Terephthalic acid esters formation |
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US11248103B2 (en) | 2019-03-20 | 2022-02-15 | 9449710 Canada Inc. | Process for the depolymerization of polyethylene terephthalate (PET) |
US11203702B1 (en) | 2019-10-17 | 2021-12-21 | National Technology & Engineering Solutions Of Sandia, Llc | Functionalized coating polymers and uses thereof |
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EP4299556A1 (de) * | 2021-04-12 | 2024-01-03 | Korea Research Institute of Chemical Technology | Verfahren zur herstellung eines terephthalatderivats durch umesterung von dimethylterephthalat |
KR102452871B1 (ko) * | 2021-04-12 | 2022-10-11 | 한국화학연구원 | 디메틸테레프탈레이트로부터 비스-(2-하이드록시에틸) 테레프탈레이트 생성하는 방법 및 이에 의한 에스테르 작용기를 포함하는 고분자의 효율적 해중합 방법 |
KR102452867B1 (ko) * | 2022-01-06 | 2022-10-11 | 한국화학연구원 | 디메틸테레프탈레이트의 에스테르 교환 반응에 의한 테레프탈레이트 유도체 제조 방법 |
CN113735817B (zh) * | 2021-11-02 | 2022-01-11 | 苏州大学 | 一种脂肪族环状低聚酯的制备方法 |
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US5407984A (en) * | 1994-08-31 | 1995-04-18 | General Electric Company | Process for preparing macrocyclic polyester oligomers |
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SU1077893A1 (ru) * | 1981-11-27 | 1984-03-07 | Всесоюзный научно-исследовательский институт синтетических и натуральных душистых веществ | Способ получени макроциклических диэфиров |
US5371112A (en) * | 1992-01-23 | 1994-12-06 | The Sherwin-Williams Company | Aqueous coating compositions from polyethylene terephthalate |
-
1996
- 1996-03-20 US US08/618,742 patent/US5668186A/en not_active Expired - Lifetime
-
1997
- 1997-01-17 ES ES97300268T patent/ES2193328T3/es not_active Expired - Lifetime
- 1997-01-17 DE DE69720579T patent/DE69720579T2/de not_active Expired - Lifetime
- 1997-01-17 EP EP19970300268 patent/EP0798336B1/de not_active Expired - Lifetime
- 1997-01-20 JP JP707497A patent/JP3715056B2/ja not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US5407984A (en) * | 1994-08-31 | 1995-04-18 | General Electric Company | Process for preparing macrocyclic polyester oligomers |
Non-Patent Citations (1)
Title |
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DATABASE WPI Section Ch, Week 8443 Derwent Publications Ltd., London, GB; Class D23, AN 84-268768 XP002044802 & SU 1 077 893 A (SYNTH NAT ESSENTIAL) , 7 March 1984 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1217023A1 (de) * | 1999-10-07 | 2002-06-26 | Kansai Paint Co., Ltd. | Verfahren zur herstellung von olefinharz |
EP1217023A4 (de) * | 1999-10-07 | 2002-09-04 | Kansai Paint Co Ltd | Verfahren zur herstellung von olefinharz |
US6686399B1 (en) | 1999-10-07 | 2004-02-03 | Kansai Paint Co., Ltd. | Process for producing alkyd resin |
US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
US7767781B2 (en) | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
US8283437B2 (en) | 2000-09-01 | 2012-10-09 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
US6713601B2 (en) | 2000-09-12 | 2004-03-30 | Cyclics Corporation | Species modification in macrocyclic polyester oligomers, and compositions prepared thereby |
WO2002068496A1 (en) * | 2001-02-28 | 2002-09-06 | E.I. Dupont De Nemours And Company | Manufacture of cyclic ester oligomers |
US6646134B2 (en) | 2001-02-28 | 2003-11-11 | E. I. Du Pont De Nemours And Company | Manufacture of cyclic ester oligomers |
US7666517B2 (en) | 2001-06-27 | 2010-02-23 | Cyclics Corporation | Isolation, formulation, and shaping of macrocyclic oligoesters |
US6831138B2 (en) | 2002-01-07 | 2004-12-14 | Cyclics Corporation | Polymer-containing organo-metal catalysts |
WO2003080705A1 (en) * | 2002-03-20 | 2003-10-02 | Cyclics Corporation | Catalytic systems |
Also Published As
Publication number | Publication date |
---|---|
DE69720579T2 (de) | 2003-11-20 |
US5668186A (en) | 1997-09-16 |
ES2193328T3 (es) | 2003-11-01 |
EP0798336B1 (de) | 2003-04-09 |
EP0798336A3 (de) | 1997-12-29 |
JP3715056B2 (ja) | 2005-11-09 |
JPH09296036A (ja) | 1997-11-18 |
DE69720579D1 (de) | 2003-05-15 |
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